CN100351211C - Ceramic moulded body comprising a photocatalytic coating and method for producing the same - Google Patents
Ceramic moulded body comprising a photocatalytic coating and method for producing the same Download PDFInfo
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- CN100351211C CN100351211C CNB038150018A CN03815001A CN100351211C CN 100351211 C CN100351211 C CN 100351211C CN B038150018 A CNB038150018 A CN B038150018A CN 03815001 A CN03815001 A CN 03815001A CN 100351211 C CN100351211 C CN 100351211C
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- Prior art keywords
- ceramic
- coating
- photocatalytic activity
- tio
- oxide
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000919 ceramic Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 title claims description 56
- 239000011248 coating agent Substances 0.000 title claims description 30
- 238000000576 coating method Methods 0.000 title claims description 30
- 229910052574 oxide ceramic Inorganic materials 0.000 claims abstract description 112
- 239000011224 oxide ceramic Substances 0.000 claims abstract description 102
- 238000005524 ceramic coating Methods 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 36
- 239000004033 plastic Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 230000003075 superhydrophobic effect Effects 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- -1 ore Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011236 particulate material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001343 alkyl silanes Chemical class 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- 238000005325 percolation Methods 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 description 15
- 238000001354 calcination Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001149 thermolysis Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- BAQNULZQXCKSQW-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4] BAQNULZQXCKSQW-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00586—Roofing materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
- C04B2111/2061—Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
- Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Devices For Post-Treatments, Processing, Supply, Discharge, And Other Processes (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Materials For Medical Uses (AREA)
- Finishing Walls (AREA)
Abstract
The invention relates to a ceramic moulded body consisting of an oxide ceramic base material and comprising a surface which self-cleans by means of water-sprinkling or percolation. Said moulded body has a porous, oxide ceramic coating which is photocatalytically active and has a specific surface of between approximately 25 m<2> /g and approximately 200 m<2>/g, preferably between approximately 40 m<2>/g and approximately 150 m<2>/g. The invention also relates to a method for producing one such ceramic moulded body.
Description
Technical field
The present invention relates to a kind of ceramic mould plastic body of oxide ceramics sill, but it has a surface with self-cleaning after water spray or the sprinkling, also relate to the manufacture method of this ceramic mould plastic body.
Background technology
EP 0 590 477B1 disclose a kind of material of construction (material of construction that for example can be used as outer wall material or roof Material), are coated with the metal oxide film of photocatalytic activity on the surface of this material of construction.The more handy sol-gel method of this metal oxide film applies.Better use TiO 2 sol to make the titanium deoxid film material of construction.The disclosed metal oxide film of EP 0 590 477B1 has the deodorizing fungicidal properties.
Because its membrane structure, the disclosed metal oxide film of EP 0 590 477B1 has low surface area, thereby has low catalytic activity.
DE 199 11 738A1 disclose a kind of titanium dioxide optical catalyst, and it is doped with Fe
3+Ion also contains and Fe
3+The equimolar amount or the pentavalent ion of equimolar amount roughly.Disclosed and the doped F e of DE 199 11 738A1
3+The ionic titanium dioxide optical catalyst makes with sol-gel method.
EP 0 909 747A1 disclose the formation method that has the surface (especially roof tiled surface) of self-cleaning properties after a kind of water spray or the watering.This surface has the dispersive height and is the hydrophobicity jut of 5-200 micron.In order to make this jut, with the dispersion liquid of inert powder material granule in siloxane solution is moistening should the surface, make the siloxanes sclerosis subsequently.EP 0 909 747A1 disclosed methods can make the ceramic body with the surface that is difficult to the adhesion dust granule.In any case the disclosed ceramic body of EP 0 909 747A1 can not have catalytic activity yet.
WO 01/79141A1 discloses a kind of formation and has had the method on surface of self-cleaning properties and the goods that make with this method.According to this method, apply from the teeth outwards drying, thermal treatment under heating up subsequently with the organometallic compound of sol-gel method with titanium oxide.Then can carry out hydrophobization to the surface of titanium oxide layer handles.
Summary of the invention
The purpose of this invention is to provide a kind of moulding bodies, roof Material especially, it has improved self-purification capacity and improved stability (for example improved wear resistance).
Another object of the present invention provides the manufacture method of this improved ceramic mould plastic body.
The objective of the invention is that ceramic mould plastic body by a kind of oxide ceramics sill reaches, but described moulding bodies has the surface of self-cleaning after a water spray or the watering, described ceramic mould plastic body has one deck porous oxide ceramic coating, and this coating has photocatalytic activity, and specific surface area is about 25m
2/ g-200m
2/ g better is about 40-150m
2/ g.
In a better example of the present invention, at least the layer of one deck band jut is arranged between described oxide ceramics sill and described porous oxide ceramic coating with photocatalytic activity, and described oxide ceramics sill has jut and/or described porous oxide ceramic coating with photocatalytic activity is the layer that one deck has jut.
In a better example of the present invention, at least one deck has the layer of jut between described oxide ceramics sill and described porous oxide ceramic coating with photocatalytic activity, described jut is to be formed by the particulate material that is fixed on the described oxide ceramics sill, described particulate material is the heatproof ground material, is selected from the ground rock, fires clay, clay, ore, ceramic powder.
In a better example of the present invention, described ceramic powder is selected from SiC, glass, glass grog and composition thereof.
In a better example of the present invention, described porous oxide ceramic coating with photocatalytic activity also comprises and is selected from Al
2O
3, SiO
2And composition thereof the oxide ceramic material of additional optical catalytic activity.
In a better example of the present invention, described median size with oxide ceramic material of photocatalytic activity is 5-100nm.
In a better example of the present invention, described median size with oxide ceramic material of photocatalytic activity is 10-50nm.
In a better example of the present invention, in described porous oxide ceramic coating with photocatalytic activity and/or oxide ceramics sill, contain TiO
2, this TiO
2Have anatase structured to small part.
In a better example of the present invention, contain TiO in described porous oxide ceramic coating with photocatalytic activity and/or the oxide ceramics sill
2, press TiO
2This TiO of total amount meter
2At least 40 weight % have anatase structured.
In a better example of the present invention, described coating has super hydrophobic surface, and the contact angle of described super hydrophobic surface and water droplet or edge angle are at least 140 °.
In a better example of the present invention, the super hydrophobic surface of described coating is with polysiloxane, alkyl silane, silicon fluoride and/or SiO
2Form.
In a better example of the present invention, the super hydrophobic surface of described coating has jut.
Purpose of the present invention can be reached by the manufacture method of the ceramic mould plastic body of oxide ceramics sill, described ceramic body have can self-cleaning after water spray or the watering the surface, described moulding bodies has photocatalytic activity, porous oxide ceramic coating, and the specific surface area of this coating is about 25-200m
2/ g better is about 40-150m
2/ g,
Described method comprises the following steps:
(a) oxide ceramic powder, conditioning agent and/or tackiness agent and a kind of liquid phase with photocatalytic activity is mixed into suspension;
(b) suspension that step (a) is made is applied on the oxide ceramics sill, forms coating;
(c) coating of cure step (b) formation, the porous oxide ceramic coating of formation photocatalytic activity.
In a better example of the present invention, at least the layer of one deck band jut is applied on the described oxide ceramics sill in a preliminary step, and the suspension that step (a) makes is applied on the oxide ceramics sill of the layer with described band jut, hardens in step (c) subsequently.
In a better example of the present invention, the viscosity modifier that described step (a) is used is a carboxymethyl cellulose.
In a better example of the present invention, the tackiness agent that uses in step (a) is a polysiloxane.
In a better example of the present invention, the described porous oxide ceramic powder with photocatalytic activity that step (a) is used also comprises and is selected from Al
2O
3, SiO
2And composition thereof material.
In a better example of the present invention, the described oxide ceramic powder with photocatalytic activity that step (a) is used is included as the particle of 5-100nm.
In a better example of the present invention, contained TiO in described oxide ceramic powder with photocatalytic activity and/or the oxide ceramics sill
2Have anatase structured to small part.
In a better example of the present invention, press TiO
2The total amount meter, contained TiO in described oxide ceramic powder with photocatalytic activity and/or the oxide ceramics sill
2At least 40 weight % have anatase structured.
In a better example of the present invention, step (c) hardened coating is carried out hydrophobization handle, form super hydrophobic surface, the contact angle of described super hydrophobic surface and water droplet or edge angle are at least 140 °.
In a better example of the present invention, use polysiloxane solution, alkyl silane and/or silicon fluoride to carry out hydrophobization and handle.
Embodiment
The ceramic mould plastic body that makes with the inventive method has suitable highly porous and stability.
The sol-gel method of the manufacturing coating of preferably using with state of the art is different, and the present invention is applied to the oxide ceramic powder of photocatalytic activity and the suspension of other auxiliary component on the oxide ceramics sill.Therefore, the inventive method does not form film, but forms the vesicular structure with high-specific surface area.
The structure that makes is the highly porous structure, and the specific surface area of porous oxide ceramic coating that is to say catalytic activity is at 25-200m
2In/g the scope, better about 40-150m
2In/g the scope.Be more preferably, specific surface area is at 40-100m
2In/g the scope.
When having about 50m
2During/g specific surface area, the oxide ceramic coating of coating can obtain gratifying high catalytic activity.The average bed thickness of oxide ceramic coating is better about 50nm to 50 micron at this moment, better about 100nm to 10 micron.When being about 1 micron, bed thickness can obtain gratifying high catalytic activity.
The porous oxide ceramic coating of photocatalytic activity of the present invention can be mould proof in advance, fungi and plant-growth, and for example photochemistry is decomposed and removed and is deposited on the ceramic mould plastic body or its inner moss, algae etc., bacterial contamination etc.The photocatalytic activity of described porous oxide ceramic coating is enough to oxidation at ambient temperature highly beneficially and decomposes described material and pollutent thus.Described material through oxidation has low viscosity, can easily remove from moulding bodies of the present invention surface upper punch in the spraying of water or towards spilling under the effect.
It is contemplated that the oxidation effect of described photocatalytically active coating acts directly on organic pollutant and the impurity on the one hand, the oxidation effect of photocatalytically active coating is by forming oxyradical on the other hand, and therefore this oxyradical also decomposes described pollutent or impurity with rear oxidation and have an effect indirectly.
If if the surface tissue below the porous oxide ceramic coating of photocatalytic activity has the surface tissue that the porous oxide ceramic coating of jut or depression and/or photocatalytic activity itself has jut and depression, then the self-purification of ceramic mould plastic body of the present invention can further strengthen.
Have found that and have jut the ceramic surface structure of (better having predetermined distribution density) has wonderful self-cleaning properties.Also can carry out the hydrophobization processing, thereby further greatly reduce the viscosity of wetting ability dirt or pollutent jut.
Can form jut by applying particulate material to the oxide ceramics sill.Better use this moment the heatproof pulverised material as described particulate material, this material better be selected from pulverizing stone, fire clay, clay, ore, ceramic powder (as silicon carbide), glass, glass grog and composition thereof.
Better use TiO
2, Al
2O
3, SiO
2And/or Ce
2O
3As described particulate material.Confirmed already that particle diameter is up to 1500nm, is preferably about 50-700nm was suitable particle.In addition, better particle diameter about 50nm to the scope of about 200nm.
Jut or the depression preferably the height or the degree of depth be up to 1500nm, better about 50-700nm, preferably about 50-200nm separately.This moment, jut also can be formed by small-particle gathering or reunion.
Can use tackiness agent that particulate material is fixed on the oxide ceramics sill.For example, the tackiness agent of use can be a polysiloxane, and it can be fixed on particulate material oxide ceramics sill surface on the one hand, provides super hydrophobic surface to the coating that forms on the other hand.Tackiness agent (for example polysiloxane) can be made in the step (a) of suspension in the present invention and add.
If keep the hydrophobicity of coatingsurface, the temperature of the cure step of step this moment (c) should be above 300 ℃.If temperature surpasses 300 ℃, then can cause the polysiloxane thermolysis, destroy the super hydrophobic surface on the porous oxide ceramic coating of photocatalytic activity.
Also can use other tackiness agent, better be organic binder bond, for example carboxymethyl cellulose.
When calcination ceramic mould plastic body (be everlasting and to about 1100 ℃ temperature range, carry out) above 300 ℃, the top layer takes place and softens in particulate material its particle surface under the effect of temperature that is used to form jut, forms the connection of sinter shape between particulate material and oxide ceramics sill.At this moment, can also for example add fusing assistant and reduce sintering temperature.
By EP 0 909 747, EP 00 115 701 and EP 1 095 023, those of ordinary skill in the art can understand the various possible methods that particulate material are fixed on the ceramic surface.The content of EP 0 909 747, EP 00,115 701 and EP 1 095 023 is drawn at this and is reference.
Be preferably, use to be selected from TiO
2, Al
2O
3, SiO
2, Ce
2O
3And composition thereof the photocatalytic activity oxide ceramic material form the porous oxide ceramic coating of photocatalytic activity.
At one preferably in the example, the oxide ceramic material of above-mentioned photocatalytic activity also can be included in the above-mentioned oxide ceramics matrix.
At one preferably in the example, in coating and/or at the oxide ceramic material of photocatalytic activity described in the oxide ceramics sill, comprise TiO
2Or Al
2O
3, and randomly combination has other oxide ceramic material.For example, mixture, aluminium dioxide and the silicon-dioxide of the mixture that titanium dioxide and silicon-dioxide are arranged, titanium dioxide and the aluminium dioxide that find to be suitable for also have the mixture of mixture, aluminum oxide and the silicon-dioxide of titanium dioxide.
Better be suitable for this moment and have anatase structured titanium dioxide as described titanium dioxide.Employed aluminum oxide better is the C aluminum oxide, and it belongs to δ-group on crystallography, and has strong oxidation catalysis effect.
A kind of appropriate C aluminum oxide can confirm already that for example AEROSIL COK 84 (mixture of a kind of 84%AEROSIL 200 and 16%C aluminum oxide) was very suitable for the present invention available from German Degussa AG.
In oxide ceramic coating, use TiO
2The time, better to small part TiO
2, better by titanium dioxide total amount at least 40 weight %, preferably the titanium dioxide of at least 70 weight %, preferred at least 80 weight % has anatase structured.
Confirmed already that the titanium dioxide with the form of mixtures that comprises about 70-85 weight % anatase octahedrite and about 30-15 weight % rutile was fit closely.
The titanium dioxide that the present invention uses is better by TiCl
4Flame hydrolysis obtains, and it is the titanium dioxide of high dispersing form, and particle diameter is preferably about 15-30nm, is preferably 21nm.
As an example, can use with the title of the P25 titanium dioxide titanium dioxide available from German Degussa AG for above-mentioned purpose, it comprises the titanium dioxide of 70% anatase octahedrite form and 30% rutile form.Preferably the uv-absorbing wavelength of the titanium dioxide of anatase octahedrite form is less than 385nm, and the uv-absorbing wavelength of the titanium dioxide of rutile form is less than 415nm.
In a better example of the present invention, ceramic mould plastic body of the present invention has a super hydrophobic surface.
Have found that then Biao Mian self-cleaning properties can be significantly improved if the porous oxide ceramic coating of above-mentioned photocatalytic activity has super hydrophobic surface.Can more easily remove the organic dirt of oxidation by water spray or watering from this surface upper punch.
In this article, term " super hydrophobic surface " is meant the surface that is at least 140 ° with the edge angle of water.Described edge angle can be measured with the water droplet that drips to lip-deep 15 microlitre volumes with ordinary method.
Described edge angle should be at least 150 °, is preferably 160 °, better is at least 170 °.
Can use Ormoceres, polysiloxane, alkyl silane and/or silicon fluoride to make the porous oxide ceramic coating hydrophobization of described photocatalytic activity.
Better apply SiO
2With the mixture of silicon fluoride, thereby form super hydrophobic surface.This hydrophobic effect or provide super hydrophobic surface advantageously to strengthen the self-cleaning properties of moulding bodies of the present invention.
In another better example, described super hydrophobic surface has jut.These juts can form with following method when applying hydrophobizing agent: particulate material is added in the hydrophobizing agent, apply the porous oxide ceramic coating of photocatalytic activity subsequently with this mixture.
After the surface being carried out the hydrophobization processing with above-mentioned hydrophobizing agent, temperature should not rise to and surpass 300 ℃, because this can cause the hydrophobizing agent thermolysis as previously described.
Therefore, only when applying hydrophobic surface, the porous oxide ceramic coating of photocatalytic activity just do not harden according to the present invention by sintering.If use polysiloxane as tackiness agent and subsequently by sinter-hardened moulding bodies, provide water repellent surface this moment if desired on the porous oxide ceramic coating of photocatalytic activity, then should need once more hydrophobization to handle usually in the surface.
Be preferably, described ceramic mould plastic body is roof sheet tile, ceramic tile, clinker tile or facade wall.
When the present invention made ceramic mould plastic body, the oxide ceramic powder of the photocatalytic activity that step (a) is used better had the nano-dispersed form.Confirmed that the particle diameter of this oxide ceramic powder is about 5-100nm, better about 10-50nm is suitable this moment.
For making ceramic mould plastic body of the present invention, form suspension very uniformly by mixing by oxide ceramic powder, conditioning agent and/or tackiness agent and liquid phase.This suspension can be applied in the required bed thickness of formation on the oxide ceramics sill.
Can be for example by topple over, brushing, spraying, throwing etc. be applied in described suspension on the oxide ceramics sill.Also the oxide ceramics sill can be immersed in this suspension.
Be preferably, the suspension that applies has bed thickness like this, and promptly behind drying and/or sintering, the porous oxide ceramic coating of the photocatalytic activity of the ceramic mould plastic body of formation is thick to be 50nm to about 50 microns, better extremely about 10 microns of about 100nm.
The about usually 0.5-100 micron of undried suspension bed thickness.
Described oxide ceramics sill can be blank (unsintered stupalith) or presintering or the agglomerating stupalith.
Better use organic viscosity modifier (for example carboxymethyl cellulose) as conditioning agent.This viscosity modifier makes suspension have required viscosity, makes it to be applied on the ceramic based material reliably by required bed thickness.Very advantageously be, surpassing 300 ℃ when carrying out calcination with hardening coat to about 1100 ℃ temperature range, described organic regulator (better carboxymethyl cellulose) burns.Because the burning of this organic regulator forms vesicular structure in the porous oxide ceramic coating of photocatalytic activity.At this moment, the best perfect combustion of organic regulator, and preferably noresidue form vesicular structure.
The calcination of the layer that step (b) makes can followingly be implemented: surpassing 300 ℃ of described moulding bodies of calcination to about 1100 ℃ temperature in incinerator or incinerator.In addition, calcination is operated under the temperature that is preferably in about 700-1100 ℃ and is carried out.
Dry can carrying out being starkly lower than under the temperature of calcination temperature.Dry normally 50-300 ℃, be preferably under 80-100 ℃ the temperature and carry out.In this temperature range, the high hydrophobicity coating that applies can not be decomposed or be impaired.
When using tackiness agent, preferably in suspension, add polysiloxane, it can the adhesion of promotes oxidn thing ceramic powder on the oxide ceramics sill.Except its adhesive effect, polysiloxane also can make the structure hydrophobization.In addition, add the viscosity that tackiness agent (for example polysiloxane) also can improve the suspension of the inventive method step (a) formation.Therefore when when suspension adds tackiness agent, need not to re-use conditioning agent in the step (a).The viscosity of using tackiness agent to regulate is enough to make the middle suspension of step (b) can be applied on the oxide ceramics sill, forms coating.
The liquid phase that is suitable for better is a water.
In a better example of the inventive method, also can in the suspension that step (a) makes, add particulate material.In another example of this method, help the jut of surperficial self-purification and the porous oxide ceramic coating of catalytic activity and in a step, make.
In the ceramic mould plastic body that another example of this method makes, it no longer comprises by the layer of one deck band jut and arranges the layer structure of separating that the porous oxide ceramic coating of catalytic activity is thereon formed, but the oxide ceramic part of jut that makes with particulate material and photocatalytic activity concerns with roughly common juxtaposed relation or mutually tight blended and exists.
Also can randomly add hydrophobizing agent to this suspension this moment, thereby make the high hydrophobization of oxide ceramic surface in the same step of this method.In this another example of described method, can only carry out cure operations, thereby the thermolysis of super hydrophobic surface does not take place by drying.
Can also earlier above-mentioned particulate material be applied on the oxide ceramics sill to form jut, and with tackiness agent and/or be fixed in by sintering on the surface of ceramic based material, use the inventive method on the surface that so forms, to form the porous oxide ceramic coating of photocatalytic activity, randomly on above-mentioned photocatalytically active coating, form super hydrophobic surface subsequently with jut.
The hydrophobizing agent that is suitable for better is the inorganic-organic hybridization molecule, for example siloxanes, especially polysiloxane.In addition, Ormoceres, alkyl silane and/or silicon fluoride have confirmed it is suitable hydrophobizing agent.
Can use suitable method to apply hydrophobizing agent, for example spray, topple over, throw, water and spill etc.For example, use preferably waterborne liquid to make hydrophobic sol or suspension mutually earlier,, then also can in this hydrophobic sol or suspension, add optional particulate material if on this super hydrophobic surface, will form jut.Available subsequently above-mentioned ordinary method applies this hydrophobic sol or suspension.
Term " super hydrophobic surface " is meant one deck high hydrophobicity layer in the present invention, and the edge angle of its water droplet is at least 140 °, better 160 °, better 170 °.
In addition, after the suspension that step (a) is made is applied on the oxide ceramics sill but before the calcination operation, also can implement predrying step.In this predrying step, can remove described liquid phase (being preferably water) by evaporation.This can realize by for example heating (for example in the forced air circulation baking oven or in the radiant dryer).Also can use other drying means, for example use microwave technology.
Proved already that predrying step was favourable, in order to avoid the layer that suspension forms in the calcination operation cracking takes place or tears.
The available method recited above in calcination operation back applies super hydrophobic surface.
At one preferably in the example, after calcination step and optional auxiliary hydrophobization are handled, can carry out aftertreatment to the porous oxide ceramic coating of the photocatalytic activity that makes.Described aftertreatment can be passed through laser, NIR or UV photoirradiation and realize.This aftertreatment can improve the viscosity between photocatalytically active coating and the oxide ceramics sill.
Find ceramic mould plastic body of the present invention except having improved self-cleaning properties, it is steady also to have improved machinery Qualitative. Huge advantage is described may making pottery with the porous oxide of the catalytic activity of super hydrophobic surface The porcelain coating sticks on the ceramic based material very securely and reliably. Therefore, for example be applied to when this coating In the time of on the roof sheet tile, if there is the people to pass by on the roof, this tile can not break or wear and tear.
Claims (23)
1. but the ceramic mould plastic body of oxide ceramics sill that has self-cleaning surface after water spray or the watering is characterized in that described moulding bodies has the porous oxide ceramic coating, and this coating has photocatalytic activity and contains TiO
2, the specific surface area of described coating is 25-200m
2/ g, described TiO
2Be by TiCl
4Polymolecularity TiO through the flame hydrolysis acquisition
2
2. ceramic mould plastic body as claimed in claim 1, it is characterized in that the layer of one deck band jut is at least arranged between described oxide ceramics sill and described porous oxide ceramic coating with photocatalytic activity, described oxide ceramics sill has jut and/or described porous oxide ceramic coating with photocatalytic activity is the layer that one deck has jut.
3. ceramic mould plastic body as claimed in claim 2, it is characterized in that between described oxide ceramics sill and described porous oxide ceramic coating with photocatalytic activity one deck at least has the layer of jut, described jut is to be formed by the particulate material that is fixed on the described oxide ceramics sill, described particulate material is the heatproof ground material, is selected from the ground rock, fires clay, clay, ore, ceramic powder.
4. ceramic mould plastic body as claimed in claim 3 is characterized in that described ceramic powder is selected from SiC, glass, glass grog and composition thereof.
5. ceramic mould plastic body as claimed in claim 1 is characterized in that described porous oxide ceramic coating with photocatalytic activity also comprises to be selected from Al
2O
3, SiO
2And composition thereof the oxide ceramic material of additional optical catalytic activity.
6. ceramic mould plastic body as claimed in claim 1 is characterized in that described median size with oxide ceramic material of photocatalytic activity is 5-100nm.
7. ceramic mould plastic body as claimed in claim 6 is characterized in that described median size with oxide ceramic material of photocatalytic activity is 10-50nm.
8. ceramic mould plastic body as claimed in claim 1 is characterized in that containing TiO in described porous oxide ceramic coating with photocatalytic activity and/or the oxide ceramics sill
2, this TiO
2Have anatase structured to small part.
9. ceramic mould plastic body as claimed in claim 8 is characterized in that containing TiO in described porous oxide ceramic coating with photocatalytic activity and/or the oxide ceramics sill
2, press TiO
2This TiO of total amount meter
2At least 40 weight % have anatase structured.
10. ceramic mould plastic body as claimed in claim 1 is characterized in that described coating has super hydrophobic surface, and the contact angle of described super hydrophobic surface and water droplet or edge angle are at least 140 °.
11. ceramic mould plastic body as claimed in claim 10, the super hydrophobic surface that it is characterized in that described coating are with polysiloxane, alkyl silane, silicon fluoride and/or SiO
2Form.
12. ceramic mould plastic body as claimed in claim 10 is characterized in that the super hydrophobic surface of described coating has jut.
13. but a manufacturing has the method for the ceramic mould plastic body of the oxide ceramics sill on self-cleaning surface after water spray or the watering, it is 25-200m that described moulding bodies has specific surface area
2The photocatalytic activity of/g contains TiO
2The porous oxide ceramic coating, described method comprises the following steps:
(a) oxide ceramic powder, viscosity modifier and/or tackiness agent and a kind of liquid phase that will have a photocatalytic activity is mixed into suspension, and described oxide ceramic powder contains TiO
2, this TiO
2Be by TiCl
4Through flame-hydrolytically produced polymolecularity TiO
2
(b) suspension that step (a) is made is applied on the oxide ceramics sill, forms coating;
(c) coating of cure step (b) formation forms the porous oxide ceramic coating with photocatalytic activity.
14. method as claimed in claim 13, it is characterized in that inciting somebody to action in a preliminary step at least, the layer of one deck band jut is applied on the described oxide ceramics sill, and the suspension that step (a) makes is applied on the oxide ceramics sill of the layer with described band jut, hardens in step (c) subsequently.
15. method as claimed in claim 13 is characterized in that the viscosity modifier that described step (a) is used is a carboxymethyl cellulose.
16. method as claimed in claim 13 is characterized in that the tackiness agent that uses is a polysiloxane in step (a).
17. method as claimed in claim 13 is characterized in that described porous oxide ceramic powder with photocatalytic activity that step (a) is used also comprises to be selected from Al
2O
3, SiO
2And composition thereof material.
18. method as claimed in claim 13 is characterized in that the described oxide ceramic powder with photocatalytic activity of step (a) use is included as the particle of 5-100nm.
19. method as claimed in claim 13 is characterized in that contained TiO in described oxide ceramic powder with photocatalytic activity and/or the oxide ceramics sill
2Have anatase structured to small part.
20. method as claimed in claim 19 is characterized in that by TiO
2The total amount meter, contained TiO in described oxide ceramic powder with photocatalytic activity and/or the oxide ceramics sill
2At least 40 weight % have anatase structured.
21. method as claimed in claim 13 is characterized in that step (c) hardened coating is carried out hydrophobization to be handled, and forms super hydrophobic surface, the contact angle of described super hydrophobic surface and water droplet or edge angle are at least 140 °.
22. method as claimed in claim 21 is characterized in that using polysiloxane solution, alkyl silane and/or silicon fluoride to carry out hydrophobization and handles.
23. by TiCl
4Through flame-hydrolytically produced polymolecularity TiO
2Purposes at the oxide ceramic coating that is used for roof sheet tile, ceramic tile, clinker tile or facade wall.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10224110.4 | 2002-05-29 | ||
| DE10224110 | 2002-05-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1662474A CN1662474A (en) | 2005-08-31 |
| CN100351211C true CN100351211C (en) | 2007-11-28 |
Family
ID=29432479
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|---|---|---|---|
| CNB038150018A Expired - Fee Related CN100351211C (en) | 2002-05-29 | 2003-05-28 | Ceramic moulded body comprising a photocatalytic coating and method for producing the same |
| CNB038149982A Expired - Fee Related CN1300063C (en) | 2002-05-29 | 2003-05-28 | Ceramic moulded body comprising a photocatalytic coating and method for producing the same |
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| CNB038149982A Expired - Fee Related CN1300063C (en) | 2002-05-29 | 2003-05-28 | Ceramic moulded body comprising a photocatalytic coating and method for producing the same |
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|---|---|
| US (2) | US20060078712A1 (en) |
| EP (2) | EP1507752B1 (en) |
| JP (2) | JP2005535544A (en) |
| CN (2) | CN100351211C (en) |
| AT (2) | ATE315542T1 (en) |
| AU (2) | AU2003243903A1 (en) |
| DE (6) | DE10393111D2 (en) |
| DK (2) | DK1507751T3 (en) |
| ES (2) | ES2256758T3 (en) |
| PL (2) | PL205816B1 (en) |
| PT (2) | PT1507752E (en) |
| RU (2) | RU2320626C2 (en) |
| SI (1) | SI1507752T1 (en) |
| WO (2) | WO2003101912A1 (en) |
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| WO1999044954A1 (en) * | 1998-03-05 | 1999-09-10 | Saint-Gobain Glass France | Substrate with photocatalytic coating |
| FR2788707A1 (en) * | 1999-01-26 | 2000-07-28 | Rhodia Chimie Sa | Treating substrates comprises treating with dispersion of photocatalytic particles and then with siliconized compound selected from siliconates and polyorganosiloxanes |
| WO2001079141A1 (en) * | 2000-04-15 | 2001-10-25 | Erlus Baustoffwerke Ag | Method for imparting a self-cleaning feature to a surface, and an object provided with a surface of this type |
| FR2816610A1 (en) * | 2000-11-10 | 2002-05-17 | Rhodia Chimie Sa | Aqueous dispersions, useful for preparation of auto-cleaning compositions for e.g. glass surfaces, comprise photocatalytic titanium dioxide particles, water soluble anionic dispersant and water soluble ampholytic film-forming polymer |
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| CN1226918A (en) * | 1996-05-31 | 1999-08-25 | 东陶机器株式会社 | Antifouling member and coating composition |
| WO1999044954A1 (en) * | 1998-03-05 | 1999-09-10 | Saint-Gobain Glass France | Substrate with photocatalytic coating |
| FR2788707A1 (en) * | 1999-01-26 | 2000-07-28 | Rhodia Chimie Sa | Treating substrates comprises treating with dispersion of photocatalytic particles and then with siliconized compound selected from siliconates and polyorganosiloxanes |
| WO2001079141A1 (en) * | 2000-04-15 | 2001-10-25 | Erlus Baustoffwerke Ag | Method for imparting a self-cleaning feature to a surface, and an object provided with a surface of this type |
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